Hair shampoo



United States Patent HAIR SHAMPOO Solomon Epstein, Chicago, Charles F. Fuchs, Evanston,

and Martell M. Gladstone, Chicago, 111., assignors to Emulsol Chemical Corporation, Chicago, Illr, acorporation of Illinois NoDrawing. Application February8; 1956" SerialNo. 564,137

Claims. (Cl. 252--152) This invention relates to hair shampoos and is especially concerned with improvements in shampoos of the liquid paste or cream type. The improved sham-- poos made in accordance with the present invention comprise those of the so-called soapless (or synthetic detergent) type and include clear as well as milky liquid or opaque types, semi-liquid and paste (gel) or cream types,

and the like.

The present invention is predicated on the discovery that, in hair shampoos of the type and utilizing detergents ofthe character hereafter described in detail, marked improvements result when certain addition agents in certain proportions are incorporated therein. These improvementsmanifest themselves in a number of respects. Thus, the use of the shampoos makes for easier manageability of the hair as has been regularly demonstrated by beauty shop operators, the hair after washing being easier to set and having a reduced tendency to tan, gling. In clear liquid shampoos, there is a definite" lowering of the cloud point. Still other advantages result depending upon the specific shampoo formulation utilized.

The addition agents referred to above comprise amides of isopropanolamine with normally liquid higher. molecular weight fatty acids such as oleic acid, linoleic acid and linolenic acid, or mixtures of higher molecular weight fatty acids which mixtures are normally liquid, that. is, liquid at normal room temperatures. Such amides are readily prepared, for example, by condensing equimolal amounts of the isopropanolamine' with the normally liquid higher molecular weight fatty acid at temperatures of about 168-180 degrees C. for several. hours. The addition agents are non-irritating to the scalp. They are, in general, possessed of a melting point just above body temperature and are readily introduced into and blend excellently with the various ingredients of the shampoos; They serve to deposit a non-sticky lubricating film on the hair. The oleic acid amide of isopropanolamine is especially satisfactory.

The detergents which are utilized in accordance with. the present invention are selected fromthe following groups. Mixtures of any two or more of any of the following detergents, with or without supplemental synthetic detergents, can also be utilized. I Y

(1) Water-soluble salts of sulfuric acidesters of aliphatic alcohols containing from 8: to 18 carbon atoms, and particularly from 12 to 14 carbon atoms. Typical examples of such detergents are the sulfates of higher aliphatic alcohols derived from coconut oil; palm kernel oil, or babassu oil, in the form of their sodium or other water-soluble salts. Such detergents are disclosed, for example, in U. S. Patent Nos. 1,968,793; 1,968,794; and 1,968,797.

(2)- Water-soluble salts of sulfuric acid. esters of aliphatic polyhydric alcohols incompletely esterified with fatty acids containing from 8 to 22 carbon atoms'and particularly from 10 to 14 carbon atoms. Typical cx-- amplesof such detergents are the mono-sulfates. of lauric acid (or coconut oil fatty. acid): monoglyceride (sodiumsalt); mono-sulfate of the lauric acid ester of diethylene glycol (sodium salt) and mono-sulfate of the myristic. acid: ester of. diglycerol (sodium salt). These detergents are disclosed in detail in Reissue Patent No. 20,636.

(3'): Water-soluble salts of alkylated. aromatic sulfonic: acids wherein the alkyl group contains a chain of from' 8 to 22 carbon atoms and particularly where the;a1kyl:- chain contains predominantly/p12 to 14 carbon atoms; Typical examples of such compounds. are thesodium salts. of an alkylate'd benzene sulfonic acid wherein the alkyli group contains approximately 12 carbon atoms and is. derived from an olefin polymer such as a propylene tetra.-- met or is derived from a kerosene fraction; the sodium salt of nonyl naphthalene sulfonic acid; and the sodium. saltof dodecyl toluene sulfonic acid; Such detergents: are disclosed in a large number of U'. S. patents typical. ofwhich are the following: 1,992,160; 2,161,173; 2,220, 099;v 2,232,117; 2,232,118; 2,233,408; and 2,283,199.

.(4) Water-soluble salts of. higher-molecular weight alkylated aromatic hydroxy-alkyl sulfuric acid esters wherein. the higherxmolecular weight alkyl radical contains from 8 t'o22 carbon. atoms and more particularlyfrom 10 to 14 carbon atoms. The higher molecular weight alkyl radical is derived from petroleum hydrocarbons, such as special cuts of kerosene, as well as from olefin polymers such as have been described, for example, hereinabove. Typical examples. of such detergents are the following:

(5) Sulfated and sulfonated vegetable oils (including mixtures of such sulfated and sulfonated oils). These are conventionally prepared from castor oil, olive oil, or oils containing glycerides of oleic acid by reaction with sulfuric acid or other sulfonating agents and then neutralizing. They are utilized in shampoos of the type which are, generally speaking, non-foaming, but they may be utilized in combination with detergents of the foaming type such as are described herein.

(6) Condensation products of hydroxy-alkyl amines. with fatty acids containing from 8 to 18 carbon atoms and wherein the molal ratio of the hydroxy-alkyl amine to the fatty acid is not substantially less than 2 to 1. Typical examples of such detergents are condensation products of 2 mols of diethanolamine with 1 mol of lauric acid or coconut oil mixed fatty acids; and condensation products of 2 mols of triethanolamine with 1 mol of lauric acid, myristic acid, or coconut oil mixed fatty acids.

' These detergents are particularly described in U'. S. Petcut No. 2,089,212.

.(7) Polyoxyalkylene glycol ethers of alkylated aromatic compounds in which the nuclear alkyl group con tains from 8 to 18 carbon atoms and more particularly;

from about 10 to 14 carbon atoms. Such detergents 'W are made, for example, by reacting an alkylated phenol or naphthol, in which the alkyl group contains from 8 to 18 carbon atoms, with an alkylene oxide, such as ethylene oxide or propylene oxide, particularly the former, to introduce several, usually from about 8 to about 20, oxyalkylene groups. A typical example is an ethylene oxide derivative of p-tert-octyl phenol in which approximately 8 to 10 oxyalkylene groups are present.

The detergent or mixture of detergents is utilized in variable proportions in the shampoo, depending upon the exact results desired and the particular nature of the formulation. In general, the detergent or mixture of detergents will fall within the range of about 8% to about 30% and, more particularly, in the range of about 15% to about 25%, by weight, of the shampoo. The amide of the isopropanolamine is utilized in minor proportions and, in most cases, the proportions thereof will fall within the range of about 1% to about 6% with a good average in the range of about 2% to about 5%, based on the weight of the shampoo. In general, the water content of the. shampoo will not fall substantially below 50% by weight of the shampoo. In the case of the paste or cream shampoos, a range of about 50 to about 65% of water and, in the case of liquid shampoos, a percentage in the range of 60 to 75% of water is satisfactory. Supplemental ingredients can, of course, be incorporated into the shampoos for obtaining special effects, such as lanolin, sulfonated lanolin, perfumes, and the like.

The following examples are illustrative of shampoos made in accordance with the present invention. It will be understood that these examples are not intended to be restrictive since numerous other non-soap or soapless formulations can be made with different of said detergents, rnixtures of said detergents, and various proportions of the ingredients, with or without supplemental ingredients, all falling within the scope of the guiding principles and teachings set forth herein. All parts listed in said examples are by weight.

Example 1 Lauryl sodium sulfate 25 Oleic acid amide of isopropanolamine 4 Water 71 Example 2 Coconut oil fatty acid mixed monoand di-glycerides,

sulfated (Na salt) 22 Oleic acid amide of isopropanolamine 3 Water Example 3 Dodecyl benzene sodium sulfonate 10 Lauryl sodium sulfate 20 Oleicacid amide of isopropanolamine 3 Water 67 Example 4 Condensation product of 2v mols diethanolamine and 1 mol lauric acid 15 Sulfonated castor oil 10 Oleic acid amide of isopropanolamine .3 Water 72 g i 3 Example 5 Sul fonated castor oil 25 Oleic acid amide of isopropanolamine 3 Water -s 72 Example 6 Polyoxyethylene glycol ether of alkylated phenol (e. g. Triton X-lOO" or Antarox A-200" or Antarox A400 1o Lauryl sodium sulfate 15 Oleic acid amide of isopropanolamine 3 Example 7 Condensation product of 2 mols diethanolamine and l mol lauric acid 7.2 Sulfosuccinic acid ester of myristic acid amide of monoethanolamine (Na salt) 28.8 Lauryl sodium sulfate 9 Oleic acid amide of isopropanolamine 3 Water 52 Example 8 Lauryl sodium sulfate 19 Lauric acid amide of monoethanolamine 1 Oleic acid amide of isopropanolamine 3 Water 77 Example 9 Mono-sulfate of coconut oil mixed fatty acid monoglycerides (Na salt) 20 Linoleic acid amide of isopropanolamine 4 Water 76 In the preparation of the shampoos, the mixture of the ingredients is heated to about 75 degrees C. with agitation until the mixture is homogeneous. While continuing the agitation, the mixture is cooled to about 30 to 35 degrees C. The perfume, if such is utilized, is added to the cooled mixture, with agitation, to effect distribution of said perfume.

This application is a continuation-in-part of application Serial No; 264,682, filed January 2, 1952, now

abandoned.

, What is claimed as new and desired to be protected by Letters Patent of the United States is:

1. An improved soapless shampoo, having a liquid to paste consistency, consisting of a mixture of at least one detergent selected from the group consisting of: (1) waters'oluble' salts of sulfuric acid esters of aliphatic alcohols containing from 8 to 18 carbon atoms; (2) Water-soluble salts of sulfuric acid esters of aliphatic polyhydric alcohols incompletely esterified with fatty acids containing from 8 to 22 carbon atoms; (3) water-soluble salts of alkylated aromatic sulfonic acids wherein the alkyl group contains a chain of from 8 to 22 carbon atoms; (4) waters oluble salts of higher molecular weight alkylated aromatic hydroxy-alkyl sulfuric acid esters wherein the higher molecular weight alkyl radical contains from 8 to 22 carbon atoms; (5) sulfonated castor oil; (6) condensation products of hydroxy-alkyl amines with fatty acids containing from 8 to 18 carbon atoms and wherein the molal ratio of the hydroxy-alkyl amine to the fatty acid is not substantially less than 2 to 1; and (7) polyoxyalkylene glycol ethers of alkylated aromatic compounds in which the nuclear alkyl group contains from 8 to 18 carbon atoms; said detergent comprising from about 8% to about 30%, by weight, of said shampoo; from about 1% to about 6%, by weight of said shampoo, of the oleic acid amide of isopropanolamine; and water, the water being present in amounts not substantially below 50%, by weight, of said shampoo, said shampoo being free from soaps.

. 2. An improved soapless shampoo, having a liquid to paste consistency, consisting of a mixture of at least one detergent selected from the group consisting of: (1) watersoluble salts of sulfuric acid esters of aliphatic alcohols containing from 8 to 18 carbon atoms; (2) water-soluble salts of sulfuric acid esters of aliphatic polyhydric alcohols incompletely esterified with fatty acids containing from 8 to 22 carbon atoms; (3) water-soluble salts of alkylated aromatic sulfonic acids wherein the alkylgroup contains a chain of from 8 to 22 carbon atoms; (4) watersoluble salts of higher molecular weight alkylated aromati'c .hydroxy-alkyl' sulfuric acid esters wherein the higher molecular weight alkyl radical-contains from 8 to 22- carbon atoms; (5) sulfonated castor oil;- (6) con- Water r 72, 76 densation products of hydroxy alkyl amines with fatty acids containing from 8 to 18 carbon atoms and wherein the molal ratio of the hydroxy-alkyl amine to the fatty acid is not substantially less than 2 to 1; and (7) polyoxyalkylene glycol ethers of alkylated aromatic compounds in which the nuclear alkyl group contains from 8 to 18 carbon atoms; said detergent comprising from about 8% to about 30%, by weight, of said shampoo; from about 1% to about 6%, by weight of said shampoo, of an amide of isopropanolamine with a normallyliquid higher molecular Weight fatty acid selected from the group consisting of oleic acid, linoleic acid, linolenic acid, and mixtures thereof; and water, the water being present in amounts not substantially below 50%, by weight, of said shampoo, said shampoo being free from soaps.

3. An improved soapless shampoo, having a liquid to paste consistency, consisting of a mixture of at least one detergent selected from the group consisting of: 1) water soluble salts of sulfuric acid esters of aliphatic alcohols containing from 8 to 18 carbon atoms; (2) water-soluble salts of sulfuric acid esters of aliphatic polyhydric alcohols incompletely esterified with fatty acids containing from 8 to 22 carbon atoms; (3) water-soluble salts of alkylated aromatic sulfonic acids wherein the alkyl group contains a chain of from 8 to 22 carbon atoms; (4) watersoluble salts of higher molecular weight alkylated aromatic hydroxy-alkyl sulfuric acid esters wherein the higher molecular weight alkyl radical contains from 8 to 22 carbon atoms; (5) sulfonated castor oil; (6) condensation products of hydroxy-alkyl amines with fatty acids containing from 8 to 18 carbon atoms and wherein the molal ratio of the hydroxy-alkyl amine to the fatty acid is not substantially less than 2 to l; and (7) polyoxyalkylene glycol ethers of alkylated aromatic compounds in which the nuclear alkyl group contains from 8 to 18 carbon atoms; said detergent comprising from about 15% to about 25%, by weight, of said shampoo; from about 2% to about 5%, by weight of said shampoo, of the oleic acid amide of isopropanolamine; and water, the water being present in amounts not substantially below 50%, by weight, of said shampoo, said shampoo being free from soaps.

4. An improved soapless shampoo, having a liquid to paste consistency, consisting of a mixture of at least one detergent selected from the group consisting of: (1) watersoluble salts of sulfuric acid esters of aliphatic alcohols containing from 8 to 18 carbon atoms; (2) water-soluble salts of sulfuric acid esters of aliphatic polyhydric alcohols incompletely esterified with fatty acids containing from 8 to 22 carbon atoms; (3) water-soluble salts of alkylated aromatic sulfonic acids wherein the alkyl group contains a chain of from 8 to 22 carbon atoms; (4) watersoluble salts of higher molecular weight alkylated aromatic hydroxy-alkyl sulfuric acid esters wherein the higher molecular weight alkyl radical contains from 8 to 22 carbon atoms; (5) sulfonated castor oil; (6) condensation products of hydroxy-alkyl amines with fatty acids containing from 8 to 18 carbon atoms and wherein the molal ratio of the hydroxy-alkyl amine to the fatty acid is not substantially less than 2 to 1; and (7) polyoxyalkylene glycol ethers of alkylated aromatic compounds in which the nuclear alkyl group contains from 8 to 18 carbon atoms; said detergent comprising from about 15% to about 25%, by weight, of said shampoo; from about 2% to about 5%, by weight of said shampoo, of the oleic acid amide of isopropanolamine; and water, the water being present in amounts of at least about by weight, of said shampoo, said shampoo being free from soaps.

5. A clear liquid soapless shampoo consisting of a mixture of at least one detergent selected from the group consisting of: (l) water-soluble salts of sulfuric acid esters of aliphatic alcohols containing from 8 to 18 car bon atoms; (2) water-soluble salts of sulfuric acid esters of aliphatic polyhydric alcohols incompletely esterified with fatty acids containing from 8 to 22 carbon atoms; (3) water-soluble salts of alkylated aromatic sulfonic acids wherein the alkyl group contains a chain of from 8 to 22 carbon atoms; (4) water-soluble salts of higher molecular weight alkylated aromatic hydroxy-alkyl sulfuric acid esters wherein the higher molecular weight alkyl radical contains from 8 to 22 carbon atoms; (5) sulfonated castor oil; (6) condensation products of hydroxyalkyl amines with fatty acids containing from 8 to 18 carbon atoms and wherein the molal ratio of the hydroxyalkyl amine to the fatty acid is not substantially less than 2 to 1; and (7) polyoxyalkylene glycol ethers of alkylated aromatic compounds in which the nuclear alkyl group contains from 8 to 18 carbon atoms; said detergent comprising from about 8% to about 30%, by weight, of said shampoo; from about 1% to about 6%, by weight of said shampoo, of the oleic acid amide of isopropanolamine whereby to lower the cloud point of said shampoo; and water, the water being present in amounts in excess of 50%, by weight, of said shampoo, said shampoo being free from soaps.

References Cited in the file of this patent Martin: The Modern Soap and Detergent Industry, vol. I, sec. V, pp. 8 and 9, The Technical Press Ltd., London, 1950. 

1. AN IMPROVED SOAPLESS SHAMPOO, HAVING A LIQUID TO PASTE CONSISTNECY, CONSISTING OF A MIXTURE OF AT LEAST ONE DETERGENT SELECTED FROM THE GROUP CONSISTING OF. (1) WATERSOLUBLE SALTS OF SULFURIC ACID ESTERS OF ALPHATIC ALCHOLS CONTAINING FROM 8 TO 18 CARBON ATOMS; (2) WATER-SOLUBLE SALTS OF SULFURIC ACID ESTERS OF ALIPHATIC POLYHYDRIC ALCOHOLS INCOMPLETELY ESTERIFIED WITH FATTY ACIDS CONTAINING FROM 8 TO 22 CARBON ATOMS; (3) WATER-SOLUBLE SALTS OF ALKYLATED ATOMATIC SULFONIC ACIDS WHEREIN THE ALKYL GROUP CONTAIN A CHAIN OF FROM 8 TO 22 CARBON ATOMS; (4) WATERSOLUBLE SALTS OF HIGHER MOLECULAR WEIGHT ALKYLATED ATOMATIC HYDROXY-ALKYL SULFURIC ACID ESTERS WHEREIN THE HIGHER MOLECULAR WEIGHT ALKYL RADICAL CONTAINS FROM 8 TO 22 CARBON ATOMS; (5) SULFONATED CASTOR OIL; (6) CONDENSATION PRODUCTS OF HYDROXY-ALKYL AIMES WITH FATTY ACIDS CONTAINING FROM 8 TO 18 CARBON ATOMS AND WHEREIN THE MOLAL RATIO OF THE HYDROXY-ALKYL AIME TO THE FATTY ACID IS NOT SUBSTANTIALLY LESS THAN 2 TO 1; AND (7) POLYOXYLKYLENE GLYCOL ETHERS OF ALKYLATED AROMATIC COMPOUNDS IN WHICH THE NUCLEAR ALKYL GROUP CONTAINS FROM 8 TO 18 CARBON ATOMS; SAID DETERGENT COMPRISING FROM ABOUT 8% TO ABOUT 30%, BY WEIGHT, OF SAID SHAMPOO, OF THE OLEIC ACID ABOUT 6%, BY WEIGHT OF SAID SHAMPOO, OF THE OLEIC ACID AMIDE OF ISOPROPANOLAMINE; AND WATER, THE WATER BEING PRESENT IN AMOUNTS NOT SUBSTANTIALLY BELOW 50%, BY WEIGHT, OF SAID SHAMPOO, SAID SHAMPOO BEING FREE FROM SOAPS. 